EP0041035A1 - Polyesters for packaging food, and process for their preparation - Google Patents

Polyesters for packaging food, and process for their preparation Download PDF

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Publication number
EP0041035A1
EP0041035A1 EP81420077A EP81420077A EP0041035A1 EP 0041035 A1 EP0041035 A1 EP 0041035A1 EP 81420077 A EP81420077 A EP 81420077A EP 81420077 A EP81420077 A EP 81420077A EP 0041035 A1 EP0041035 A1 EP 0041035A1
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EP
European Patent Office
Prior art keywords
polycondensation
crystallization
intrinsic viscosity
precursor
ppm
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Application number
EP81420077A
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German (de)
French (fr)
Other versions
EP0041035B2 (en
EP0041035B1 (en
Inventor
Claude Bonnebat
Gilbert Roullet
Yves Vaginay
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Rhodia Chimie SAS
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Rhone Poulenc Specialites Chimiques
Rhone Poulenc Chimie SA
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Application filed by Rhone Poulenc Specialites Chimiques, Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Specialites Chimiques
Priority to AT81420077T priority Critical patent/ATE10375T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1397—Single layer [continuous layer]

Definitions

  • the present invention relates to a saturated polyester based on ethylene glycol terephthalate units for containers for food use.
  • the invention also relates to its process for obtaining.
  • polyester bottles intended to contain aerated mineral waters must have an acetaldehyde content in their wall less than 5 ppm (parts per million of polyester by weight / weight) for a volume of between 1 liter and 2 liters if one wants to ensure that under storage conditions, at temperatures up to 45 ° C, the amount of acetaldehyde capable of migrating into the liquid remains below the detectable organoleptic threshold, i.e. 40-50 ppb (parts per billion by weight / weight of liquid).
  • the polymer is crystallized by heating to 180-220 ° C and the post-condensation is carried out at a temperature above the crystallization temperature.
  • the present invention therefore relates to a polyethylene terephthalate having useful characteristics for injection molding or extrusion blow molding of transparent articles, as well as a process for obtaining said polyterephthalate.
  • ethylene terephthalate units is also meant the small amount of di- and tri-ethylene glycol terephthalate inevitably formed during polycondensation.
  • polyesters from aromatic dicarboxylic acids or their functional derivatives and from aliphatic diols by direct esterification or transesterification then polycondensation in the presence of catalysts is a known process.
  • the dicarboxylic acid is esterified or its dimethyl ester is transesterified by glycol.
  • the polycondensation of the diglycolic ester formed is carried out.
  • a low molecular weight polyester is obtained which will be designated below by the term "precursor”.
  • the precursor is dried, crystallized and then subjected to post-condensation in the solid or molten state until the desired final viscosity is obtained.
  • di- and / or tri-ethylene glycol it is essential that the total amount which can either be added or result from its in situ formation by dehydration of excess ethylene glycol remains less than 3.5% in moles by moles of diacid residues engaged in the chain.
  • the use of very small quantities of trifunctional acid or alcohol compounds is possible insofar as this addition does not increase the rate of crystallization of the polymer. Isophthalic acid has been found to be particularly favorable.
  • the catalytic system used can influence the formation of acetaldehyde. It is not recommended to use the catalysts in excessive quantity.
  • Antimony compounds as a polycondensation catalyst at contents below 250 ppm (expressed by weight of metal relative to the amount of all the constituents) has been found to be particularly favorable.
  • the degree of polycondensation of the precursor depends on factors such as the nature and the rate of the catalytic system, the performance of the apparatus, the temperature and the pressure of the polycondensation. This degree of polycondensation can be determined by measuring the intrinsic viscosity of the polymer. Under given operating conditions there is a maximum polycondensation threshold, beyond which the viscosity can no longer be increased, the degradation reactions taking on a preponderant importance over the polycondensation reaction.
  • the polyterephthalates obtained according to the invention can be molded into containers by any process. They can be molded by injection, extrusion, injection blow molding or extrusion blow molding either directly into a finished product, or indirectly into a tube or preform which will subsequently be molded to the shape of the desired container.
  • a precursor is prepared by transesterification from a mixture of dimethyl terephthalate, ethylene glycol and polycondensation in the presence of 3% isophthalic acid (in moles).
  • a catalytic system based on manganese phosphorus, antimony containing 200 ppm of antimony is used.
  • the granules After post-condensation in the solid state until an IV of 0.81 dl / g is obtained, the granules have the following characteristics:
  • Example 1 is repeated by adding 4 mol% of diethylene glycol to the reaction products.
  • the polycondensation is stopped at a value of VI p at 0.60 dl / g - VI ⁇ is 0.70 dl / g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Wrappers (AREA)
  • Peptides Or Proteins (AREA)
  • Detergent Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Auxiliary Devices For And Details Of Packaging Control (AREA)
  • Containers And Plastic Fillers For Packaging (AREA)

Abstract

Novel polyester for the packaging of perishable comestibles, e.g., as bottles for still or carbonated mineral waters, is a poly(ethylene glycol)terephthalate (PET) having an intrinsic viscosity ranging from 0.65 to 1.05 dl/g and a density of more than 1.38, comprising 92.5 to 98.5% of ethylene terephthalate recurring units and 1.5 to 7.5 mol % of recurring units of at least one polybasic acid and/or polyhydric alcohol comonomeric crystallization retardant, the di- and/or triethylene glycol content thereof being less than about 3.5 mol % per mol of diacid radicals present in the polymer chain, said PET also having a residual acetaldehyde concentration of less than 1.25 ppm, with acetaldehyde being reformed therefrom at a rate of less than 5 ppm/hour, at 220 DEG C., and said PET being devoid of visible crystallization in an at least 4 mm thick test plate shaped in a mold cavity from a melt thereof.

Description

La présente invention concerne un polyester saturé à base d'unités de téréphtalate d'éthylène glycol pour récipients à usage alimentaire. L'invention se rapporte également à son procédé d'obtention.The present invention relates to a saturated polyester based on ethylene glycol terephthalate units for containers for food use. The invention also relates to its process for obtaining.

On sait que les polyesters thermoplàstiques constitués de motifs de téréphtalate d'éthylène glycol constituent des matières premières intéressantes pour le conditionnement de denrées alimentaires sous forme de films, feuilles, récipients et notamment de bouteilles destinées à la conservation de liquides plats ou de boissons gazeuses.It is known that thermoplastic polyesters made up of ethylene glycol terephthalate units constitute useful raw materials for the packaging of foodstuffs in the form of films, sheets, containers and in particular bottles intended for the preservation of flat liquids or carbonated drinks.

L'une des qualités essentielles à laquelle doit répondre un emballage et plus particulièrement une bouteille est sa transparence et sa brillance. Par étirage a partir de l'état amorphe dans des conditions de biorientation, le polytéréphtalate d'éthylène glycol conserve une bonne transparence tout en bénéficiant d'une phase cristalline orientée qui renforce considérablement ses propriétés mécaniques et permet une réduction de la perméabilité aux gaz. La transparence et la brillance peuvent cependant être affectées par la formation de spherolites cristallins notamment dans le cas de récipients à parois relativement épaisses. La réalisation de bouteilles par injection et/ou extrusion-soufflage passe nécessairement par la réalisation d'une préforme à parois épaisses obtenue par trempe à partir de l'état fondu et la formation de spherolites cristallins au stade de la préforme affecte la transparence de l'objet fini. Il s'est donc revélé avantageux de proposer des grades de polyester ayant une faible vitesse de cristallisation.One of the essential qualities to which packaging and more particularly a bottle must respond is its transparency and shine. By stretching from the amorphous state under biorienting conditions, polyethylene terephthalate retains good transparency while benefiting from an oriented crystalline phase which considerably strengthens its mechanical properties and allows a reduction in gas permeability. Transparency and gloss can however be affected by the formation of crystalline spherolites, in particular in the case of containers with relatively thick walls. The production of bottles by injection and / or extrusion blow molding necessarily involves the production of a thick-walled preform obtained by quenching from the molten state and the formation of crystalline spherolites at the preform stage affects the transparency of the 'finished object. It has therefore been found to be advantageous to offer polyester grades having a low crystallization speed.

Une autre qualité à laquelle doit repondre un emballage en matière polymère est l'absence de tout composé susceptible de migrer dans la denrée alimentaire ou la boisson et d'en altérer le goût ou l'odeur. On sait que les résines polyesters libèrent par dégradation de l'acétaldehyde qui présente une forte odeur et un goût caractéristique et qui se manifeste. à des teneurs extrêmement faibles.Another quality to which a packaging made of polymer material must respond is the absence of any compound liable to migrate into the foodstuff or beverage and to alter its taste or odor. It is known that polyester resins release by degradation of acetaldehyde which has a strong odor and a characteristic taste and which manifests itself. at extremely low levels.

Ce problème est particulièrement important pour le conditionnement des eaux minérales. Ainsi les bouteilles en polyester destinées à contenir des eaux minérales gazeuses doivent avoir une teneur en acétaldéhyde dans leur paroi inférieure à 5 ppm (parties par million de polyester en poids/poids) pour un volume compris entre 1 litre et 2 litres si l'on veut s'assurer que dans les conditions de stockage, à des températures pouvant atteindre 45°C, la quantité d'acétaldehyde susceptible de migrer dans le liquide reste inférieure au seuil organoleptique détectable, soit 40-50 ppb (parties par milliard en poids/poids de liquide). L'origine de l'acétaldehyde dans les objets finis dépend à la fois de la quantité résiduelle présente dans le granulé de polyester, avant sa transformation, et de la quantité formée au cours de la transformation à l'état fondu par suite d'une dégradation dans les conditions de cisaillement et de températures requises pour le moulage.This problem is particularly important for the conditioning of mineral waters. Thus polyester bottles intended to contain aerated mineral waters must have an acetaldehyde content in their wall less than 5 ppm (parts per million of polyester by weight / weight) for a volume of between 1 liter and 2 liters if one wants to ensure that under storage conditions, at temperatures up to 45 ° C, the amount of acetaldehyde capable of migrating into the liquid remains below the detectable organoleptic threshold, i.e. 40-50 ppb (parts per billion by weight / weight of liquid). The origin of acetaldehyde in finished articles depends both on the residual quantity present in the polyester granule, before its transformation, and on the quantity formed during the transformation in the molten state as a result of a degradation in shear and temperature conditions required for molding.

On a déjà proposé divers procédés pour diminuer la teneur et/ou la reformation d'acétaldehyde des résines de polytéréphtalate d'éthylène glycol. D'une manière générale ces procédés décrivent des conditions opératoires au cours des phases de séchage, cristallisation ou post-condensation du précurseur telles qu'elles sont appliquées couramment pour l'obtention de résines de haute viscosité.Various methods have already been proposed for reducing the content and / or reformation of acetaldehyde in polyethylene terephthalate resins. In general, these methods describe operating conditions during the drying, crystallization or post-condensation phases of the precursor as they are commonly applied for obtaining high viscosity resins.

Ainsi selon la demande de brevet français publiée 78.23635 le séchage des copeaux de polyester est effectué à 180-230*C pendant 4 à 12 heures en. atmosphère inerte pour abaisser la teneur en acétaldéhyde dans les copeaux à moins de 2,5 ppm. D'après la demande de brevet français 79.10061 on obtient une diminution de la vitesse de formation d'acétaldéhyde par traitement à l'état fondu sous atmosphère inerte du polyester complètement polymérisé.Thus, according to the French published patent application 78.23635 drying polyester chips is carried out at 180-230 ° C for 4 to 12 hours. inert atmosphere to lower the acetaldehyde content in the chips to less than 2.5 ppm. According to French patent application 79.10061, a reduction in the rate of acetaldehyde formation is obtained by treatment in the molten state under an inert atmosphere of the fully polymerized polyester.

Selon la demande de brevet français 79.11981 on cristallise le polymère par chauffage à 180-220°C et la post-condensation est réalisée à une température supérieure à la température de cristallisation.According to French patent application 79.11981, the polymer is crystallized by heating to 180-220 ° C and the post-condensation is carried out at a temperature above the crystallization temperature.

Le brevet américain 4.154.920 décrit un procédé en deux étapes à partir d'un prépolymère de viscosité intrinsèque 0,1 à 0,3 dl/g selon lequel le prépolymère est d'abord condensé à l'état fondu en couche mince puis post-condensé à l'état solide.American patent 4,154,920 describes a two-step process starting from a prepolymer of intrinsic viscosity 0.1 to 0.3 dl / g according to which the prepolymer is first condensed in the state melted in a thin layer then post-condensed in the solid state.

Enfin d'après la demande de brevet français 79.12337 les pastilles de polyester sont post-condensées et stabilisées par chauffage à 180-220°C durant 2 à 20 heures dans l'air, augmentant la viscosité intrinsèque jusqu'à une valeur comprise entre 0,60 et 0,97 dl/g.Finally according to French patent application 79.12337 the polyester pellets are post-condensed and stabilized by heating at 180-220 ° C for 2 to 20 hours in air, increasing the intrinsic viscosity to a value between 0 , 60 and 0.97 dl / g.

La demanderesse a trouvé que la quantité d'acétaldéhyde présente dans les parois d'un article moulé, et susceptible de migrer, c'est-à-dire la quantité résiduelle présente dans les granulés additionnée à la quantité réformée lors de la transformation à l'état fondu en article moulé ne dépendait pas seulement des conditions de traitement du précurseur (séchage cristallisation et post-condensation) mais était liée d'une part à la qualité intrinsèque du précurseur, obtenu dans la phase initiale de la polycondensation à l'état fondu, et d'autre part à la caractéristique de recristallisation du polymère lors de l'opération de trempe à l'état fondu.The Applicant has found that the quantity of acetaldehyde present in the walls of a molded article, and capable of migrating, that is to say the residual quantity present in the granules added to the quantity reformed during the transformation with l melt state in molded article did not depend only on the conditions of treatment of the precursor (drying crystallization and post-condensation) but was linked on the one hand to the intrinsic quality of the precursor, obtained in the initial phase of polycondensation in the state molten, and secondly to the characteristic of recrystallization of the polymer during the quenching operation in the molten state.

Le précurseur doit en effet contenir le plus petit nombre possible de sites initiateurs d'une dégradation ultérieure : vinylique, carboxylique. Pour un même système catalytique, en fonction des conditions de la polycondensation, les qualités intrinsèques de la résine peuvent être très différentes. La stabilité thermique du précurseur peut se mesurer indirectement par la mesure de la vitesse de reformation d'acétaldéhyde du polymère porté à haute température. Par ailleurs la quantité d'acétaldéhyde reformée est directement liée à la température de mise en oeuvre du matériau et celleci sera d'autant plus élevée que la vitesse de recristallisation sera plus grande lors de la trempe.The precursor must in fact contain the smallest possible number of sites which initiate subsequent degradation: vinyl, carboxylic. For the same catalytic system, depending on the conditions of the polycondensation, the intrinsic qualities of the resin can be very different. The thermal stability of the precursor can be measured indirectly by measuring the rate of acetaldehyde reformation of the polymer brought to high temperature. Furthermore, the quantity of acetaldehyde reformed is directly linked to the processing temperature of the material and this will be all the higher the faster the recrystallization rate during the quenching.

La présente invention a donc pour objet un polytéréphtalate d'éthylène glycol ayant des caractéristiques utiles pour le moulage par injection ou extrusion-soufflage d'articles transparents, ainsi qu'un procédé pour l'obtention dudit polytéréphtalate.The present invention therefore relates to a polyethylene terephthalate having useful characteristics for injection molding or extrusion blow molding of transparent articles, as well as a process for obtaining said polyterephthalate.

Le polytéréphtalate d'éthylène glycol selon l'invention, de viscosité intrinsèque comprise entre 0,65 et 1,05 dl/g et de densité > 1,38, est constitué de 92,5 à 98,5 % de motifs téréphtalate -d'éthylène et de 1,5 5 à 7,5 % en moles de· motifs d'un agent retardateur de cristallisation choisi parmi un ou plusieurs polyacides et/ou polyalcools, la quantité de di- et/ou tri- éthylène glycol étant limitée à une valeur inférieure à environ 3,5 % (moles par moles de restes diacides présents dans la chaine) et est caractérisé par les propriétés suivantes prises en combinaison :

  • - teneur résiduelle en acétaldéhyde inférieure à 1,25 ppm
  • - vitesse de réformation d'acétaldehyde à 220°C inférieure à 5 ppm/heure,
  • - absence dé cristallisation visible dans une plaque d'épaisseur au moins égale à 4 mm obtenue par injection du matériau fondu à 280°C dans un moule dont les parois sont maintenues à une température égale à 37°C.
The polyethylene terephthalate according to the invention, with an intrinsic viscosity of between 0.65 and 1.05 dl / g and a density> 1.38, consists of 92.5 to 98.5% of terephthalate -d units ethylene and from 1.5 5 to 7.5 mol% of · units of a crystallization retarding agent chosen from one or more poly acids and / or polyalcohols, the amount of di- and / or tri-ethylene glycol being limited to a value less than about 3.5% (moles per moles of diacid residues present in the chain) and is characterized by the following properties taken in combination:
  • - residual acetaldehyde content of less than 1.25 ppm
  • - acetaldehyde reforming rate at 220 ° C less than 5 ppm / hour,
  • absence of visible crystallization in a plate with a thickness at least equal to 4 mm obtained by injection of the molten material at 280 ° C. in a mold whose walls are maintained at a temperature equal to 37 ° C.

On entend par motifs téréphtalate d'éthylène également la faible quantité de téréphtalate de di- et tri- éthylène glycol inévitablement formés lors de la polycondensation.By ethylene terephthalate units is also meant the small amount of di- and tri-ethylene glycol terephthalate inevitably formed during polycondensation.

La fabrication des polyesters à partir d'acides dicar- boxyliques aromatiques ou de leurs dérivés fonctionnels et de diols aliphatiques par estérification directe ou transestérification puis polycondensation en présence de catalyseurs est un procédé connu. Dans une première étape de réaction l'acide dicarboxylique est estérifié ou son ester diméthylique est transestérifié par le glycol. Dans une seconde étape on procède à la polycondensation de l'ester diglycolique formé. On obtient un polyester de bas poids moléculaire que l'on désignera ci-après par le terme "précurseur". Pour obtenir des polyesters de poids moléculaire élevé le précurseur est séché, cristallisé puis soumis à une post-condensation à l'état solide ou fondu jusqu'à l'obtention de la viscosité finale désirée.The manufacture of polyesters from aromatic dicarboxylic acids or their functional derivatives and from aliphatic diols by direct esterification or transesterification then polycondensation in the presence of catalysts is a known process. In a first reaction step, the dicarboxylic acid is esterified or its dimethyl ester is transesterified by glycol. In a second step, the polycondensation of the diglycolic ester formed is carried out. A low molecular weight polyester is obtained which will be designated below by the term "precursor". To obtain high molecular weight polyesters, the precursor is dried, crystallized and then subjected to post-condensation in the solid or molten state until the desired final viscosity is obtained.

Pour l'obtention du polytéréphtalate d'éthylène glycol selon l'invention, le procédé est caractérisé en ce que pour la formation du précurseur d'une viscosité intrinsèque comprise entre 0,55 et 0,70 dl/g,la polycondensation est réalisée en présence d'au moins un modifiant copolymérisable retardateur de cristallisation en quantité comprise entre 1,5 et 7,5 % en moles par rapport l'ensemble diacide ou diester + retardateur, à une température inférieure à 290°C et est limitée à un degré compris entre 75 et 90% du degré de polycondensation maximal accessible évalué d'après la viscosité intrinsèque du polymère.To obtain the polyethylene terephthalate according to the invention, the process is characterized in that for the formation of the precursor with an intrinsic viscosity of between 0.55 and 0.70 dl / g, the polycondensation is carried out in presence of at least one copolymerizable modifier retarding crystallization in an amount of between 1.5 and 7.5 mol% relative to the diacid or diester + retarder assembly, at a temperature below 290 ° C. and is limited to one degree between 75 and 90% of the maximum accessible degree of polycondensation evaluated according to the intrinsic viscosity of the polymer.

Les modifiants copolymérisables retardateurs de cristallisation peuvent être des polyacides carboxyliques aromatiques et/ou aliphatiques et/ou des polyalcools. On peut utiliser par exemple les acides isophtalique, naphtalène dicarboxylique, adipique, sébacique ou leurs dérivés fonctionnels pouvant former des polyesters. Des exemples de diols sont le néopentyl glycol, l'hexane diol-1,6, le bis-hydroxyméthyl-1,4 cyclohexane, le diéthylène glycol, le triéthylène glycol. S'agissant du di- et/ou tri-éthylène glycol il est essentiel que la quantité totale qui peut soit être ajoutée, soit résulter de sa formation in situ par déshydratation de l'éthylène glycol en excès reste inférieure à 3,5% en moles par moles de restes diacides engagés dans la chaine. L'emploi de très faibles quantités de composés trifonctionnels acides ou alcools est possible dans la mesure où cette addition n'augmente pas la vitesse de cristallisation du polymère. L'acide isophtalique a été trouvé particulièrement favorable.The copolymerizable modifiers which retard crystallization can be aromatic and / or aliphatic polycarboxylic acids and / or polyalcohols. Isophthalic, naphthalene dicarboxylic, adipic, sebacic acids or their functional derivatives which can form polyesters can be used, for example. Examples of diols are neopentyl glycol, hexane diol-1,6, bis-hydroxymethyl-1,4 cyclohexane, diethylene glycol, triethylene glycol. With regard to di- and / or tri-ethylene glycol it is essential that the total amount which can either be added or result from its in situ formation by dehydration of excess ethylene glycol remains less than 3.5% in moles by moles of diacid residues engaged in the chain. The use of very small quantities of trifunctional acid or alcohol compounds is possible insofar as this addition does not increase the rate of crystallization of the polymer. Isophthalic acid has been found to be particularly favorable.

Le système catalytique utilisé peut avoir une influence sur la formation de l'acétaldehyde. Il est déconseillé d'utiliser les catalyseurs en quantité excessive. Les composés de l'antimoine comme catalyseur de polycondensation à des teneurs inférieures à 250 ppm (exprimé en poids de métal par rapport à la quantité de tous les constituants) a été trouvé particulièrement favorable.The catalytic system used can influence the formation of acetaldehyde. It is not recommended to use the catalysts in excessive quantity. Antimony compounds as a polycondensation catalyst at contents below 250 ppm (expressed by weight of metal relative to the amount of all the constituents) has been found to be particularly favorable.

Le degré de polycondensation du précurseur dépend de facteurs tels que la nature et le taux du système catalytique, les performances de l'appareillage, la température et la pression de la polycondensation. Ce degré de polycondensation peut être déterminé par la mesure de la viscosité intrinsèque du polymère. Dans des conditions opératoires données il existe un seuil de polycondensation maximum, au-delà duquel la viscosité ne peut plus être augmentée, les réactions de dégradation prenant une importance prépondérante sur la réaction de polycondensation.The degree of polycondensation of the precursor depends on factors such as the nature and the rate of the catalytic system, the performance of the apparatus, the temperature and the pressure of the polycondensation. This degree of polycondensation can be determined by measuring the intrinsic viscosity of the polymer. Under given operating conditions there is a maximum polycondensation threshold, beyond which the viscosity can no longer be increased, the degradation reactions taking on a preponderant importance over the polycondensation reaction.

Selon l'un des moyens particuliers essentiel de l'invention la viscosité intrinsèque du précurseur VIp est limitée à une valeur comprise entre 0,75 et 0,90 de la viscosité maximale possible VI∞, c'est-à-dire à la relation :

Figure imgb0001
According to one of the essential particular means of the invention, the intrinsic viscosity of the precursor VIp is limited to a value between 0.75 and 0.90 of the maximum possible viscosity VI∞, that is to say the relation :
Figure imgb0001

Si la viscosité atteinte est limitée en-dessous de 0,75 VI∞ , le procédé n'est pas performant. Si la polycondensation est poursuivie au-delà de la valeur 0,90 VI∞] on observe une augmentation de la vitesse de reformation en acétaldehyde.If the viscosity reached is limited below 0.75 VI∞, the process is not efficient. If the polycondensation is continued beyond the value 0.90 VI∞], an increase in the rate of reformation into acetaldehyde is observed.

Après cristallisation et séchage du précurseur obtenu selon le procédé de l'invention, la post-condensation peut être réalisée par tout procédé connu pour obtenir une viscosité intrinsèque finale comprise entre environ 0,65 et 1,05. La post-condensation est de préférence réalisée à l'état solide sous vide poussé ou sous gaz inerte entre 190 et 230°C pendant une durée pouvant varier de 5 à 25 heures. Le produit obtenu peut être transformé en copeaux, granulés ou pastilles par des moyens connus.After crystallization and drying of the precursor obtained according to the process of the invention, the post-condensation can be carried out by any known process to obtain a final intrinsic viscosity of between approximately 0.65 and 1.05. Post-condensation is preferably carried out in the solid state under high vacuum or under inert gas between 190 and 230 ° C for a period which can vary from 5 to 25 hours. The product obtained can be transformed into chips, granules or pellets by known means.

Les polytéréphtalates obtenus selon l'invention peuvent être moulés en récipients par tous procédés. Ils peuvent être moulés par injection, extrusion, injection-soufflage ou extrusion-soufflage soit directement en un produit fini, soit indirectement en un tube ou préforme qui sera ultérieurement moulé à la forme du récipient souhaitée.The polyterephthalates obtained according to the invention can be molded into containers by any process. They can be molded by injection, extrusion, injection blow molding or extrusion blow molding either directly into a finished product, or indirectly into a tube or preform which will subsequently be molded to the shape of the desired container.

Du fait de leur vitesse de recristallisation réduite lors de la trempe, ils permettent de mouler des articles transparents à parois relativement épaisses tels que des préformes pour bouteilles avec une dégradation minimale de la résine. Ils présentent un intérêt tout particulier pour la.réalisation de bouteilles destinées au conditionnement des eaux minérales qui peuvent être stockées pendant une durée prolongée sans altération sensible de goût.Due to their reduced recrystallization speed during quenching, they make it possible to mold transparent articles with relatively thick walls such as preforms for bottles with minimal degradation of the resin. They are of particular interest for the production of bottles intended for the conditioning of mineral waters which can be stored for a prolonged period without appreciable alteration of taste.

Les exemples qui suivent illustrent l'invention. Il doit être bien entendu qu'ils ne sont pas donnés à titre limitatif et que toutes variantes ou modifications peuvent être apportées sans pour autant sortir du cadre général de la présente invention.The following examples illustrate the invention. It should be understood that they are not given by way of limitation and that all variants or modifications can be made without departing from the general scope of the present invention.

Les méthodes de mesure suivantes ont été utilisées pour caractériser le produit selon l'invention.The following measurement methods were used to characterize the product according to the invention.

  • - Taux résiduel en acétaldéhyde : AA résiduel. On broie l'échantillon refroidi sous de l'azote liquide en une poudre fine, inférieure à 800 microns. La poudre est chauffée 1h30 à 160°C en ballon fermé sous azote et la quantité d'acétaldéhyde libérée est dosée par chromatographie en phase vapeur (CPV).- Residual acetaldehyde level: residual AA. The cooled sample is ground under liquid nitrogen to a fine powder, less than 800 microns. The powder is heated for 1 hour 30 minutes at 160 ° C. in a closed flask under nitrogen and the quantity of acetaldehyde released is determined by vapor phase chromatography (CPV).
  • - Vitesse de reformation d'acétaldéhyde à 220°C : Cette mesure est effectuée sur la poudre broyée comme précédemment. La poudre est chauffée 30 minutes jusqu'à 220°C de manière à éliminer l'acétaldéhyde résiduel initialement présent. Le ballon est purgé à l'azote et fermé. On prélève un échantillon de gaz après 1, 2, 3 heures de chauffage et on dose l'acétaldéhyde sur chaque échantillon par CPV. La quantité totale est divisée par le temps (3 heures) pour donner le nombre de parties en poids d'acétaldéhyde par million en poids de polyester par heure.- Acetaldehyde reformation rate at 220 ° C: This measurement is carried out on the ground powder as above. The powder is heated for 30 minutes to 220 ° C. so as to remove the residual acetaldehyde initially present. The flask is purged with nitrogen and closed. A gas sample is taken after 1, 2, 3 hours of heating and the acetaldehyde is assayed on each sample by CPV. The total amount is divided by time (3 hours) to give the number of parts by weight of acetaldehyde per million by weight of polyester per hour.
  • - Viscosité intrinsèque VI en dl/g : la mesure est effectuée à 25°C en solution à 1 % (poids/volume) dans un mélange phénol/ orthochlorophénol 47/53.- Intrinsic viscosity VI in dl / g: the measurement is carried out at 25 ° C in 1% solution (weight / volume) in a phenol / orthochlorophenol 47/53 mixture.
  • - Cristallisation : On plastifie le polymère sec à 290°C de manière à détruire tout germe de cristallisation.- Crystallization: The dry polymer is plasticized at 290 ° C so as to destroy any germ of crystallization.

On injecte le produit fondu dans une série de moules dont l'épaisseur varie progressivement pour obtenir des plaques d'épais- Seur comprise entre 2 et 5 mm. La température des parois du moule est conditionnée à 37°C. On note à quelle épaisseur e apparait un léger trouble correspondant à un début de cristallisation. Plus l'épaisseur e des. pièces amorphes, totalement transparentes, est grande, plus la vitesse de recristallisation est faible.Injecting the molten product into a series of molds whose thickness varies gradually to obtain thick- S eur plates between 2 and 5 mm. The temperature of the mold walls is conditioned at 37 ° C. We note at what thickness e appears a slight haze corresponding to the beginning of crystallization. The greater the thickness e of. amorphous parts, completely transparent, is large, the lower the speed of recrystallization.

- Teneur en diéthylène glycol (DEG %) : L'échantillon est broyé et saponifié par la potasse en solution éthanolique. L'analyse est effectuée par chromatographie gaz en présence d'un étalon interne. Les résultats sont exprimés en moles par rapport aux restes diacides.- Diethylene glycol content (DEG%): The sample is ground and saponified by potassium hydroxide in ethanolic solution. The analysis is carried out by gas chromatography in the presence of an internal standard. The results are expressed in moles relative to the diacid residues.

EXEMPLE 1 :EXAMPLE 1:

On prépare un précurseur par transestérification à partir d'un mélange de diméthyltéréphtalate, éthylène glycol et polycondensation en présence de 3 % d'acide isophtalique (en moles). On utilise un système catalytique à base de manganèse phosphore, antimoine contenant 200 ppm d'antimoine.A precursor is prepared by transesterification from a mixture of dimethyl terephthalate, ethylene glycol and polycondensation in the presence of 3% isophthalic acid (in moles). A catalytic system based on manganese phosphorus, antimony containing 200 ppm of antimony is used.

On arrête la polycondensation quand la viscosité intrinsèque du précurseur VIp atteint 0,61 dl/g, la viscosité limite VI∞ pouvant être amenée jusqu'à une valeur de 0,72 dl/g. Après séchage et cristallisation les granulés sont post-condensés à l'état solide sous 66,66 Pa pendant 12 heures à 217°C pour obtenir une VI de 0,81 dl/g.

Figure imgb0002
The polycondensation is stopped when the intrinsic viscosity of the precursor VI p reaches 0.61 dl / g, the limiting viscosity VI∞ being able to be brought to a value of 0.72 dl / g. After drying and crystallization the granules are post-condensed in the solid state at 66.66 Pa for 12 hours at 217 ° C to obtain an IV of 0.81 dl / g.
Figure imgb0002

EXEMPLE 2 :EXAMPLE 2:

On renouvelle l'exemple_1 à la différence que l'on ajoute 2 % d'acide isophtalique.Example 1 is repeated, except that 2% isophthalic acid is added.

On arrête la polycondensation à une valeur VIp de 0,65 dl/g. La VI∞ est de 0,75 dl/g.The polycondensation is stopped at a value VI p of 0.65 dl / g. The VI∞ is 0.75 dl / g.

Après post-condensation à l'état solide jusqu'à obtention d'une VI de 0,81 dl/g les granulés présentent les caractéristiques suivantes :

Figure imgb0003
After post-condensation in the solid state until an IV of 0.81 dl / g is obtained, the granules have the following characteristics:
Figure imgb0003

EXEMPLES COMPARATIFSCOMPARATIVE EXAMPLES EXEMPLE 3 :EXAMPLE 3:

On prépare un homopolymère par transestérification. de diméthyltéréphtalate et d'éthylène glycol, puis polycondensation en utilisant le même système catalytique que dans l'exemple précédent. On arrête la polycondensation à une valeur VIp égale à 0,60, la VI∞ étant de 0,72. Le précurseur est traité dans les conditions de l'exemple 1 jusqu'à l'obtention d'une viscosité finale de 0,75 dl/g. On obtient les caractéristiques suivantes :

Figure imgb0004
A homopolymer is prepared by transesterification. dimethyl terephthalate and ethylene glycol, then polycondensation using the same catalytic system as in the previous example. The polycondensation is stopped at a value VI p equal to 0.60, the VI∞ being 0.72. The precursor is treated under the conditions of Example 1 until a final viscosity of 0.75 dl / g is obtained. The following characteristics are obtained:
Figure imgb0004

EXEMPLE 4 :EXAMPLE 4:

On répète l'opération de l'exemple 1 (addition de 3 % d'acide isophtalique) mais la viscosité VI est poussée au maximum possible soit 0,72. Après post-condensation dans les mêmes conditions, on obtient les résultats suivants :

Figure imgb0005
The operation of Example 1 is repeated (addition of 3% isophthalic acid) but the viscosity VI is pushed to the maximum possible is 0.72. After post-condensation under the same conditions, the following results are obtained:
Figure imgb0005

EXEMPLE 5 :EXAMPLE 5:

On reproduit l'exemple 1 en ajoutant 4 % en moles de diéthylène glycol aux produits réactionnels. On arrête la polycondensation à une valeur de VIp à 0,60 dl/g - VI∞ est de 0,70 dl/g. Après séchage, cristallisation et post-condensations dans les conditions décrites on obtient les résultats suivants :

Figure imgb0006
Example 1 is repeated by adding 4 mol% of diethylene glycol to the reaction products. The polycondensation is stopped at a value of VI p at 0.60 dl / g - VI∞ is 0.70 dl / g. After drying, crystallization and post-condensing under the conditions described, the following results are obtained:
Figure imgb0006

Les polyesters obtenus selon les exemples 1 à 5 sont utilisés pour la fabrication de bouteilles biorientées.The polyesters obtained according to Examples 1 to 5 are used for the manufacture of bi-oriented bottles.

A cet effet les granulés sont séchés à moins de 50 ppm d'humidité et injectés à l'état fondu à l'aide d'une presse à injection au travers d'un moule de préformes à canaux chauds de manière à obtenir des préformes amorphes de 47 g, d'une épaisseur de parois de 3,8 mm. On mesure la teneur en acétaldéhyde sur un échantillon prélevé sur la paroi de la préforme. Pour chacun des essais on note la température d'injection du matériau et le % d'AA mesuré sur la préforme (poids/poids polyester).

Figure imgb0007
To this end, the granules are dried at less than 50 ppm of humidity and injected in the molten state using an injection press through a mold of hot-channel preforms so as to obtain amorphous preforms. 47 g, with a wall thickness of 3.8 mm. The acetaldehyde content is measured on a sample taken from the wall of the preform. For each of the tests, the injection temperature of the material and the% of AA measured on the preform (weight / weight polyester) are noted.
Figure imgb0007

Les préformes sont soufflées à la température de biorientation en bouteilles de 1,5 litre de capacité. Les bouteilles sont remplies d'eau minérale gazeuse et stockées à 45°C. Un test organoleptique effectué comparativement à une eau minérale stockée en bouteille de verre ne révèle aucune modification de goût pouvant résulter d'une migration de l'acétaldéhyde après un mois de stockage pour la bouteille obtenue à partir du polytéréphtalate selon les exemples 1 et 2. Dans tous les autres cas, on détecte une altération sensible du goût à partir de 8 jours de stockage, ce qui rend l'eau minérale impropre à la consommation.The preforms are blown at biorientation temperature in 1.5 liter capacity bottles. The bottles are filled with sparkling mineral water and stored at 45 ° C. An organoleptic test carried out in comparison with mineral water stored in a glass bottle does not reveal any change in taste which may result from migration of acetaldehyde after one month of storage for the bottle obtained from the polyterephthalate according to Examples 1 and 2. In all other cases, a significant change in taste is detected from 8 days of storage, which makes the mineral water unfit for consumption.

Claims (11)

1. Polytéréphtalate d'éthylène glycol ayant une viscosité intrinsèque comprise entre 0,65 et 1,05 dl/g et une densité supérieure à 1,38, constitué de 92,5 à 98,5 % de motifs téréphtalate d'éthylène et de 1,5 à 7,5 % en moles de motifs d'un agent retardateur de cristallisation choisi parmi un ou plusieurs polyacides et/ou polyalcools, la quantité de di- et/ou tri- éthylène glycol étant limitée à une valeur inférieure à environ 3,5 % (moles par moles de restes diacides présents dans la chaine), caractérisé par les propriétés suivantes prises en combinaison : - teneur résiduelle en acétaldéhyde inférieure à 1,25 ppm - vitesse de reformation d'acétaldéhyde à 220°C inférieure à 5 ppm/heure - absence de cristallisation visible dans une plaque d'épaisseur au moins égale à 4 mm obtenue par injection du matériau fondu à 280°C dans un moule dont les parois sont maintenues à une température égale à 37°C. 1. Polyterephthalate of ethylene glycol having an intrinsic viscosity of between 0.65 and 1.05 dl / g and a density greater than 1.38, consisting of 92.5 to 98.5% of ethylene terephthalate units and 1.5 to 7.5 mole% of units of a crystallization retarding agent chosen from one or more polyacids and / or polyalcohols, the amount of di- and / or triethylene glycol being limited to a value less than approximately 3.5% (moles per moles of diacid residues present in the chain), characterized by the following properties taken in combination: - residual acetaldehyde content of less than 1.25 ppm - acetaldehyde reformation rate at 220 ° C less than 5 ppm / hour - Absence of visible crystallization in a plate of thickness at least equal to 4 mm obtained by injection of the molten material at 280 ° C in a mold whose walls are maintained at a temperature equal to 37 ° C. 2. Polytéréphtalate d'éthylène glycol selon la revendication 1, caractérisé en ce que les motifs de l'agent retardateur de cristallisation sont dérivés de l'acide isophtalique.2. Polyterephthalate of ethylene glycol according to claim 1, characterized in that the units of the agent for retarding crystallization are derived from isophthalic acid. 3. Procédé de préparation de polytéréphtalate d'éthylène glycol par estérification ou transestérification de l'acide téréphtalique ou de ses dérivés fonctionnels par l'éthylène glycol et polycondensation en présence de catalyseurs, jusqu'à obtention d'un précurseur puis post-condensation du précurseur jusqu'à une viscosité intrinsèque comprise entre 0,65 et 1,05 dl/g, caractérisé en ce que pour là formation du précurseur d'une viscosité intrinsèque comprise entre environ 0,55 et environ 0,70 dl/g la polycondensation est réalisée en présence d'au moins un modifiant copolymérisable retardateur de cristallisation en quantité comprise entre 1,5 . et 7,5 % (en moles par rapport à l'ensemble diacide ou diester + retardateur) à une température inférieure à 290°C et est limitée à un degré compris entre 75 et 90 % du degré de polycondensation maximal accessible évalué d'après la viscosité intrinsèque.3. Process for the preparation of polyethylene terephthalate by esterification or transesterification of terephthalic acid or of its functional derivatives with ethylene glycol and polycondensation in the presence of catalysts, until a precursor is obtained then post-condensation of the polycondensation for precursor up to an intrinsic viscosity between 0.65 and 1.05 dl / g, characterized in that for the formation of the precursor with an intrinsic viscosity between about 0.55 and about 0.70 dl / g is carried out in the presence of at least one copolymerizable modifier retarding crystallization in an amount between 1.5. and 7.5% (in moles relative to the diacid or diester + retarder combination) at a temperature below 290 ° C and is limited to a degree between 75 and 90% of the maximum accessible degree of polycondensation evaluated according to intrinsic viscosity. 4. Procédé selon la revendication 3, caractérisé en ce que l'on utilise un catalyseur de polycondensation à base d'antimoine à des teneurs inférieures à 250 ppm.4. Method according to claim 3, characterized in that a polycondensation catalyst based on anti monk at contents lower than 250 ppm. 5. Emploi du polytéréphtalate selon l'une quelconque des. revendications 1 à 4 pour le moulage d'articles d'emballages destinés au conditionnement de denrées alimentaires.5. Use of the polyterephthalate according to any one of. Claims 1 to 4 for the molding of packaging articles intended for the packaging of foodstuffs. 6. Emploi du polytéréphtalate selon l'une quelconque des revendications 1 à 4 pour la fabrication de bouteilles biorientées destinées au conditionnement des eaux minérales plates ou gazeuses.6. Use of the polyterephthalate according to any one of claims 1 to 4 for the manufacture of bioriented bottles intended for the conditioning of still or sparkling mineral waters. 1. Procédé de préparation de polytéréphtalate d'éthylène glycol par estérification ou transestérification de l'acide téréphtalique ou de ses dérivés fonctionnels par l'éthylène glycol et polycondensation en présence de catalyseurs, jusqu'à obtention d'un précurseur puis post-condensation du précurseur jusqu'à une viscosité intrinsèque comprise entre 0,65 et 1,05 dl/g, caractérisé en ce que pour la formation du précurseur d'une viscosité intrinsèque comprise entre 0,55 et environ 0,70 dl/g la polycondensation est réalisée en présence d'au moins un modifiant copolymérisable retardateur de cristallisation en quantité comprise entre 1,5 et 7,5 % (en moles par rapport à l'ensemble diacide ou diester + retardateur) à une température inférieure à 290°C et est limitée à un degré compris entre 75 et 90 % du degré de polycondensation maximal.accesible évalué d'après la viscosité intrinsèque.1. Process for the preparation of polyethylene terephthalate by esterification or transesterification of terephthalic acid or of its functional derivatives with ethylene glycol and polycondensation in the presence of catalysts, until a precursor is obtained then post-condensation of the precursor up to an intrinsic viscosity between 0.65 and 1.05 dl / g, characterized in that for the formation of the precursor with an intrinsic viscosity between 0.55 and about 0.70 dl / g the polycondensation is carried out in the presence of at least one copolymerizable modifier retarding crystallization in an amount of between 1.5 and 7.5% (in moles relative to the diacid or diester + retarder) at a temperature below 290 ° C. and is limited to a degree between 75 and 90% of the maximum degree of polycondensation. accessible evaluated according to the intrinsic viscosity. 2. Procédé selon la revendication.1, caractérisé en ce que le modifiant copolymérisable ratardateur de cristallisation est l'acide isophtalique, l'acide naphtalène dicarboxylique, l'acide adipique, l'acide sébacique, le néopentylglycol, l'hexanediol-1,6, le bis-hydroxyméthyl-1,4 cyclohexane, le diéthylèneglycol, le triéthylèneglycol ou un mélange de ces composés.2. Method according to claim.1, characterized in that the modifiable copolymerizable modifier is crystallization isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, neopentyl glycol, hexanediol-1, 6, bis-hydroxymethyl-1,4 cyclohexane, diethylene glycol, triethylene glycol or a mixture of these compounds. 3. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que l'on utilise un catalyseur de polycondensation à base d'antimoine à des teneurs inférieures à 250 ppm.3. Method according to any one of claims 1 and 2, characterized in that one uses a polycondensation catalyst based on antimony at contents lower than 250 ppm. 4. Emploi du polytéréphtalate obtenu selon-le procédé décrit dans l'une quelconque des revendications 1 à 3 pour le moulage d'articles d'emballages destinés au conditionnement de denrées alimentaires.4. Use of the polyterephthalate obtained according to the process described in any one of claims 1 to 3 for the molding of packaging articles intended for the packaging of foodstuffs. 5. Emploi du polytéréphtalate obtenu selon le procédé décrit dans l'une quelconque des revendications 1 à 3 pour la fabrication de bouteilles biorientées destinées au conditonnement des eaux minérales plates ou gazeuses.5. Use of the polyterephthalate obtained according to the process described in any one of claims 1 to 3 for the manufacture of bioriented bottles intended for the packaging of still or sparkling mineral waters.
EP81420077A 1980-05-20 1981-05-19 Polyesters for packaging food, and process for their preparation Expired - Lifetime EP0041035B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81420077T ATE10375T1 (en) 1980-05-20 1981-05-19 POLYESTER FOR FOOD PACKAGING AND PROCESS FOR THEIR MANUFACTURE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8011201A FR2482971A1 (en) 1980-05-20 1980-05-20 POLYESTERS FOR FOOD PACKAGES AND PROCESS FOR OBTAINING THEM
FR8011201 1980-05-20

Publications (3)

Publication Number Publication Date
EP0041035A1 true EP0041035A1 (en) 1981-12-02
EP0041035B1 EP0041035B1 (en) 1984-11-21
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JP (1) JPS5716024A (en)
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ES (1) ES8300121A1 (en)
FR (1) FR2482971A1 (en)
MX (1) MX166409B (en)
PT (1) PT73056B (en)

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FR2679238A1 (en) * 1991-07-15 1993-01-22 Mitsubishi Chem Ind COPOLYESTER OF TEREPHTHALIC ACID AND ETYLENE GLYCOL AND HOLLOW RECIPIENT AND STRETCH FILM MADE THEREFROM.
EP0595185A1 (en) * 1992-10-26 1994-05-04 Hoechst Celanese Corporation Modified polyethylene terephthalate
EP0625539A1 (en) * 1992-12-04 1994-11-23 Toray Industries, Inc. Thermal lamination polyester film
US5419936A (en) * 1989-11-24 1995-05-30 Ici Chemical Industries Plc Polyester bottles
EP0697428A2 (en) 1994-08-19 1996-02-21 Ems-Inventa Ag Process for the preparation of linear w-carboxylic acid unit containing copolyesters
WO1998049217A1 (en) * 1997-05-01 1998-11-05 Eastman Chemical Company Process for the preparation of polyesters
EP0943649A2 (en) * 1998-03-17 1999-09-22 SINCO RICERCHE S.p.A. Stabilized polyester resins having reduced formaldehyde content
FR2828199A1 (en) * 2001-07-31 2003-02-07 Perrier Vittel Man Technologie Polyethylene terephthalate polyester useful for making hollow containers, e.g. bottles, has a low intrinsic viscosity and a low acetaldehyde content
EP2168751A1 (en) 2008-09-29 2010-03-31 Nestec S.A. Method of making a container such as a bottle from a preform made of thermoplastic polymer
WO2013034950A1 (en) * 2011-09-08 2013-03-14 Société Anonyme Des Eaux Minerales D'evian Method for producing a bio-pet polymer
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US4560741A (en) * 1985-04-12 1985-12-24 Eastman Kodak Company Polyester resins capable of forming containers having improved gas barrier properties
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US5256363A (en) * 1987-03-26 1993-10-26 Mitsui Petrochemical Industries, Ltd. Polyethylene terephthalate and uses thereof
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US6268026B1 (en) 1997-10-20 2001-07-31 Hoechst Celanese Corporation Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same
US6312772B1 (en) 1997-10-20 2001-11-06 Hoechst Celanese Corporation Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer
US6426128B1 (en) 1998-01-06 2002-07-30 Hna Holdings, Inc. Co-processable multi-layer laminates for forming high strength, haze-free, transparent articles and methods of producing same
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MXPA02003932A (en) 1999-10-27 2003-03-27 Coca Cola Co Process for reduction of acetaldehyde and oxygen in beverages contained in polyester based packaging.
FR2828129A1 (en) * 2001-07-31 2003-02-07 Perrier Vittel Man Technologie Use of a polyethylene terephthalate resin with a low intrinsic viscosity to make preforms and containers, especially water bottles
FR2830788B1 (en) * 2001-10-12 2006-09-22 Tergal Fibres METHOD FOR MANUFACTURING HOLLOW BODIES, HOLLOW BODIES, PREFORMS AND BOTTLES OBTAINED BY THIS PROCESS
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EP1433804A1 (en) * 2002-12-03 2004-06-30 Nan Ya Plastics Corp. Copolyester composition for manufacturing large volume polyester bottle
US7303795B2 (en) 2003-03-13 2007-12-04 Invista North America S.A. R.L. Molding of polypropylene with enhanced reheat characteristics
US7368523B2 (en) * 2004-11-12 2008-05-06 Eastman Chemical Company Polyester polymer and copolymer compositions containing titanium nitride particles
US20060051542A1 (en) * 2004-09-03 2006-03-09 Zhiyong Xia Polyester polymer and copolymer compositions containing metallic molybdenum particles
US7662880B2 (en) * 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles
US7816436B2 (en) * 2004-11-08 2010-10-19 INVISTA North America S.à.r.l. Carbon black with large primary particle size as reheat additive for polyester and polypropylene resins
US20060105129A1 (en) * 2004-11-12 2006-05-18 Zhiyong Xia Polyester polymer and copolymer compositions containing titanium carbide particles
US7300967B2 (en) * 2004-11-12 2007-11-27 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic titanium particles
US20060122300A1 (en) * 2004-12-07 2006-06-08 Zhiyong Xia Polyester polymer and copolymer compositions containing steel particles
US20060222795A1 (en) * 2005-03-31 2006-10-05 Howell Earl E Jr Polyester polymer and copolymer compositions containing particles of one or more transition metal compounds
US8557950B2 (en) 2005-06-16 2013-10-15 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
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US7776942B2 (en) * 2005-09-16 2010-08-17 Eastman Chemical Company Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
US9777111B2 (en) * 2005-10-20 2017-10-03 Grupo Petrotemex, S.A. De C.V. PET polymer with improved properties
US7358324B2 (en) 2005-12-06 2008-04-15 Dak Americas Llc Manufacturing method of co-polyester resins for clear mono-layer containers with improved gas barrier characteristics
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CA2647633A1 (en) * 2006-03-29 2007-10-04 Nestle Waters Management & Technology Method for the direct production of polyester articles for packaging purposes and articles obtained therefrom
US20070260002A1 (en) * 2006-05-04 2007-11-08 Zhiyong Xia Titanium nitride particles, methods of making them, and their use in polyester compositions
US20080058495A1 (en) * 2006-09-05 2008-03-06 Donna Rice Quillen Polyester polymer and copolymer compositions containing titanium and yellow colorants
US20090186177A1 (en) * 2008-01-22 2009-07-23 Eastman Chemical Company Polyester melt phase products and process for making the same
DE102009010597A1 (en) * 2008-07-12 2010-01-14 Epc Industrial Engineering Gmbh Process for the production of polyester, in particular linear polyester, for textile yarns and textile fibers and for bottles and equipment for carrying out the process
EP3878887A1 (en) 2009-03-03 2021-09-15 The Coca-Cola Company Method of making a bio-based polyethylene terephthalate
CN101948567A (en) * 2010-09-01 2011-01-19 华润包装材料有限公司 Modified copolyester used for producing gas-containing soft drink packaging product and preparation method thereof
EP2747981B1 (en) * 2011-08-25 2017-03-01 Plastipak Packaging, Inc. Extruded pet parison
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CA2941491C (en) 2014-03-11 2022-05-31 Furanix Technologies B.V. Process for enhancing the molecular weight of a polyester
NL2015265B1 (en) 2015-08-04 2017-02-21 Furanix Technologies Bv Polyester composition.
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0181498A1 (en) * 1984-10-12 1986-05-21 Teijin Limited Process for preparation of high-molecular weight polyester
US5419936A (en) * 1989-11-24 1995-05-30 Ici Chemical Industries Plc Polyester bottles
US5529744A (en) * 1989-11-24 1996-06-25 Imperial Chemical Industries Plc Method for the production of polymer bottles
US5409983A (en) * 1990-06-15 1995-04-25 Imperial Chemical Industries Plc Refillable bottle of polyethylene terephthalate copolymer and its manufacture
EP0693356A3 (en) * 1990-06-15 1997-09-10 Ici Plc Polyester polymer products
EP0465040A1 (en) * 1990-06-15 1992-01-08 Imperial Chemical Industries Plc Polyester polymer products
US5262513A (en) * 1991-07-15 1993-11-16 Mitsubishi Kasei Corporation Copolyester, and hollow container and stretched film made thereof
FR2679238A1 (en) * 1991-07-15 1993-01-22 Mitsubishi Chem Ind COPOLYESTER OF TEREPHTHALIC ACID AND ETYLENE GLYCOL AND HOLLOW RECIPIENT AND STRETCH FILM MADE THEREFROM.
EP0595185A1 (en) * 1992-10-26 1994-05-04 Hoechst Celanese Corporation Modified polyethylene terephthalate
EP0625539A1 (en) * 1992-12-04 1994-11-23 Toray Industries, Inc. Thermal lamination polyester film
EP0625539A4 (en) * 1992-12-04 1997-01-15 Toray Industries Thermal lamination polyester film.
EP0697428A2 (en) 1994-08-19 1996-02-21 Ems-Inventa Ag Process for the preparation of linear w-carboxylic acid unit containing copolyesters
US5656700A (en) * 1994-08-19 1997-08-12 Ems--Inventa Ag Process for preparing linear copolyesters containing omega-hydroxycarboxylic acid units
US6048957A (en) * 1997-05-01 2000-04-11 Eastman Chemical Company Process for polyesters with improved properties
WO1998049217A1 (en) * 1997-05-01 1998-11-05 Eastman Chemical Company Process for the preparation of polyesters
EP0943649A2 (en) * 1998-03-17 1999-09-22 SINCO RICERCHE S.p.A. Stabilized polyester resins having reduced formaldehyde content
US6057016A (en) * 1998-03-17 2000-05-02 Sinco Ricerche S.P.A. Polyester resins with improved properties
EP0943649A3 (en) * 1998-03-17 2001-02-07 SINCO RICERCHE S.p.A. Stabilized polyester resins having reduced formaldehyde content
FR2828199A1 (en) * 2001-07-31 2003-02-07 Perrier Vittel Man Technologie Polyethylene terephthalate polyester useful for making hollow containers, e.g. bottles, has a low intrinsic viscosity and a low acetaldehyde content
WO2003011940A1 (en) * 2001-07-31 2003-02-13 Nestle Waters Management & Technology (Societe Anonyme) Low intrinsic viscosity and low acetaldehyde content polyester, hollow preforms and containers obtained from said polymer
US7189441B2 (en) 2001-07-31 2007-03-13 Nestle Waters Management & Technology Low intrinsic viscosity and low acetaldehyde content polyester, hollow preforms and containers obtained from said polymer
EP2168751A1 (en) 2008-09-29 2010-03-31 Nestec S.A. Method of making a container such as a bottle from a preform made of thermoplastic polymer
WO2013034950A1 (en) * 2011-09-08 2013-03-14 Société Anonyme Des Eaux Minerales D'evian Method for producing a bio-pet polymer
WO2013034743A1 (en) * 2011-09-08 2013-03-14 Societe Anonyme Des Eaux Minerales D'evian Et En Abrege "S.A.E.M.E" Method for producing a bio-pet polymer
CN103842404A (en) * 2011-09-08 2014-06-04 埃维昂矿泉水有限公司 Method for producing a bio-pet polymer
US9695276B2 (en) 2011-09-08 2017-07-04 SOCIETE ANONYME DES EAUX MINERALES D'EVIAN et en abrégé“S.A.E.M.E.” Method for producing a bio-pet polymer
EP2753652B1 (en) 2011-09-08 2020-07-22 Societe Anonyme des Eaux Minerales d'Evian Et en Abrege "S.A.E.M.E" Method for producing a bio-pet polymer
US11028221B2 (en) 2015-12-11 2021-06-08 SOCIETE ANONYME DES EAUX MINERALES D'EVIAN et en abrégé “S.A.E.M.E” PET polymer with an anti-crystallization comonomer that can be bio-sourced

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US4340721B1 (en) 1998-12-01
EP0041035B2 (en) 1992-03-18
EP0041035B1 (en) 1984-11-21
PT73056B (en) 1982-07-01
BR8103108A (en) 1982-02-09
ES502313A0 (en) 1982-10-01
PT73056A (en) 1981-06-01
US4340721A (en) 1982-07-20
ES8300121A1 (en) 1982-10-01
KR840000468B1 (en) 1984-04-09
ATE10375T1 (en) 1984-12-15
AU7065681A (en) 1981-11-26
FR2482971A1 (en) 1981-11-27
JPS5716024A (en) 1982-01-27
FR2482971B1 (en) 1985-04-12
CA1164144A (en) 1984-03-20
MX166409B (en) 1993-01-07
AU540702B2 (en) 1984-11-29
DE3167283D1 (en) 1985-01-03
JPH0121167B2 (en) 1989-04-20
KR830006372A (en) 1983-09-24

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